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Title: Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

Abstract

Here, a series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C5Me5)2Th(Cl)[P(Mes)2] (Mes = mesityl = 2,4,6-(CH3)3C6H2; dark red-purple), (C5Me5)2Th[P(Mes)(CH3)]2 (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)2] (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th(Cl)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th[P(Mes)(SiMe3)]2 (orange), and (C5Me5)2Th[PH(Mes)]2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.

Authors:
 [1];  [2];  [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Missouri, Columbia, MO (United States). Dept. of Chemistry
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. at Buffalo, NY (United States). Dept. of Chemistry
  3. Univ. at Buffalo, NY (United States). Dept. of Chemistry
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1483515
Report Number(s):
LA-UR-18-22942
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 12; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rungthanaphatsophon, Pokpong, Duignan, Thomas J., Myers, Alexander J., Vilanova, Sean P., Barnes, Charles L., Autschbach, Jochen, Batista, Enrique R., Yang, Ping, and Walensky, Justin R. Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b00922.
Rungthanaphatsophon, Pokpong, Duignan, Thomas J., Myers, Alexander J., Vilanova, Sean P., Barnes, Charles L., Autschbach, Jochen, Batista, Enrique R., Yang, Ping, & Walensky, Justin R. Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes. United States. doi:10.1021/acs.inorgchem.8b00922.
Rungthanaphatsophon, Pokpong, Duignan, Thomas J., Myers, Alexander J., Vilanova, Sean P., Barnes, Charles L., Autschbach, Jochen, Batista, Enrique R., Yang, Ping, and Walensky, Justin R. Fri . "Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes". United States. doi:10.1021/acs.inorgchem.8b00922. https://www.osti.gov/servlets/purl/1483515.
@article{osti_1483515,
title = {Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes},
author = {Rungthanaphatsophon, Pokpong and Duignan, Thomas J. and Myers, Alexander J. and Vilanova, Sean P. and Barnes, Charles L. and Autschbach, Jochen and Batista, Enrique R. and Yang, Ping and Walensky, Justin R.},
abstractNote = {Here, a series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C5Me5)2Th(Cl)[P(Mes)2] (Mes = mesityl = 2,4,6-(CH3)3C6H2; dark red-purple), (C5Me5)2Th[P(Mes)(CH3)]2 (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)2] (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th(Cl)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th[P(Mes)(SiMe3)]2 (orange), and (C5Me5)2Th[PH(Mes)]2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.},
doi = {10.1021/acs.inorgchem.8b00922},
journal = {Inorganic Chemistry},
number = 12,
volume = 57,
place = {United States},
year = {2018},
month = {6}
}

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Figures / Tables:

Figure 1 Figure 1: Thermal ellipsoid plots of 1 (left) and 4 (right) shown at the 50% probability level. The hydrogen atoms have been omitted for clarity.

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Works referencing / citing this record:

CCDC 1834568: Experimental Crystal Structure Determination: QIBSIG : bis(η5-pentamethylcyclopentadienyl)-(bis(2,4,6-trimethylphenyl)phosphanyl)-chloro-thorium(iv)
dataset, April 2018

  • Rungthanaphatsophon, Pokpong; Duignan, Thomas; Myers, Alexander
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc1zl0m6

CCDC 1834571: Experimental Crystal Structure Determination: QIBTED : bis(η5-pentamethylcyclopentadienyl)-(bis(2,4,6-trimethylphenyl)phosphanyl)-methyl-thorium(iv)
dataset, April 2018

  • Rungthanaphatsophon, Pokpong; Duignan, Thomas; Myers, Alexander
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc1zl0q9

Thorium(IV) and Uranium(IV) Phosphaazaallenes
journal, August 2019

  • Rungthanaphatsophon, Pokpong; Fajen, O. Jonathan; Kelley, Steven P.
  • Inorganics, Vol. 7, Issue 9
  • DOI: 10.3390/inorganics7090105

Thorium(IV) and Uranium(IV) Phosphaazaallenes
journal, August 2019

  • Rungthanaphatsophon, Pokpong; Fajen, O. Jonathan; Kelley, Steven P.
  • Inorganics, Vol. 7, Issue 9
  • DOI: 10.3390/inorganics7090105

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.